The Absorption Laws and Measurment of Absorption

Intensity

(a) Absorption laws: The absorption of light by the molecules is governed by

the following laws:

Lambert's law:
It states that the fraction of the monochromatic light absorbed by a
homogeneous medium is independent of the intensity of the incident light and
each successive unit layer absorbs an equal fraction of light incident on it.

Beer's law: It states that the fraction of the incident monochromatic light
absorbed is proportional to the number of absorbing molecules in the light- path
and will increase with increasing concentration or sample thickness, i;e., path
length.

From these laws, the following empirical expression, known as Beer-Lambert

law, may be formulated.
 log (I/IO) = εcL = A

where Io = intensity of the incident light;

I = intensily of. the transmitted light;
ε = molar absorptivity or molar extinction coefficient (L mol-1,cm-1);
c = concentration (moles/Litre);
L= path length (cm)
A = absorbance

Validity of Beer’s Law:

The Beer-Lambert law is rigorously obeyed provided a single species gives rise
to the observed absorption.

However, the law may not be valid when

 different forms due to association, dissociation or polymerisation of the

absorbing species are in equilibrium.

 solute and solvent interactions occur generating new species.

 There is a thermal equilibrium between ground electronic state and a low -

lying excited state.
 The compounds are charged by irradiation (fluorescent compounds).

 monochromatic light is not used.

 The solution contains some suspension.

(b) Measurement of absorption intensity Molar extinction coefficient (ε):

The molar extinction coefficient (ε) is a measure of the intensity of absorption

and is reported as such or as its logarithm (log ε)

The intensity of absorption is directly proportional to the transition probability. A

fully allowed transition will have ε values greater than 104 while those with low
transition probability will have ε values less than 103
Units of ε : We know that ε = A/cL. Putting the units of A, c and L we get,
ε = l/(mol /Litre x cm; = Litremol-1 cm
However, by-convention these units are rarely used.
SOME USEFUL TERMS

(a) CHROMOPHORES:

 Originally the term chromophere was used for a system which imparts
colour to a compound (Chromophorus = colour carrier). The coloured
substances owe their colour to the presence of one or more unsaturated
groups responsible for electronic absorption. These groups are called
chromophores, e.g., C=C, C≡C, C≡N, C=O, N≡N, etc. Chromophores are of
two types:

(i) Chromophores having -electrons. They undergo * transitions. e.g.,

>C=C<, -C≡C etc.

(ii) Chromophores having both n and - electons. They undergo n*

transitions in addition to * transitions. e.g., >C=O, -N=N-, -NO2, etc.
(B) AUXOCHROMES:
 An auxochrome is an auxiliary group which does not absorb itself but
interacts with the chromophore causing a change in the wavelength as
well as intensity of absorption

 e.g., amino and substituted amino goups (-NH2, -NHR and –NR2), hydroxy
and alkoxy groups.

 In general, an auxochrome is a group that deepens colour.

 its presence causes a shift in the UV or visible absorption maximum to a

longer wavelength.

Reason:
 Auxochrome provide additional opportunity for charge delocalization and
thus molecule require smaller energy for transition to excited states.
Stabilization of the * excited state brings the lowest energy excited state closer
to the highest energy ground state and thus requires a lower energy (long
wavelength) for transition.

(c) BATHOCHROMIC SHIFT (RED SHIFT):

Shift to longer wavelength: It is produced by

 A change of medium (* transitions undergo bathochromic shift with an

increase in the polarity of the solvent).

 When an auxochrome is attached to a carbon-carbon double bond. E.g.,

ethylene absorbs at 175 nm in comparison to 1-butene. (λmax = 185 nm) or
isobutene (λmax = 188 nm). The bathochromic shift increases as the number
of alkyl groups increases.

 Availability of n-electrons: Conversion of phenol to the corresponding anion

results in a bathochromic shift of the E2, and B bands of benzene with an
increase in εmax because the non-bonding electrons in the anion are
available for interaction with -electron system of the ring.
(d) HYPSOCHROMIC SHIFT

Blue shift-Shift to shorter wavelength: This may be caused by

 A change of medium (n  * transitions undergo hypsochromic shift with an

increase in the polarity of solvent). For example, acetone absorbs at 279 nm
in hexane while in water it absorbs at 264.5 nm. This blue shift results from
hydrogen bonding which lowers energy of the n-orbital.

 Availability of n-electrons: When an auxochrome is attached to double bonds

where n electrons are available (e.g., C=O).

 The hypsochromic shift of the n  * transitionis primarily due to -I effect of

the heteroatom i.e., O, N or Cl, which increases the energy gap between n
and * orbitals and hence absorption shift towards shorter wavelength.
(e) HYPERCHROMIC EFFECT- High intensity:

 This effect leads to increased absorption intensity (ε value)

 Bathochromic shift is often accompanied by hyperchromic effect.

 For example, the intensities of primary and secondary bands of phenol are
increased in phenolate anion

(F) HYPOCHROMIC EFFECT: Low intensity:

 It is the effect leading to decreased absorption intensity.

 Hypsochromic shifts are often accompanied by hypochromic effect.

 For example, the intensity of primary and secondary bands of benzoic acid
are decreased in benzoate anion
EFFECT OF CONJUGATION ON THE UV SPECTRA OF DIFFERENT TYPES
OF DIENES (OR POLYENES).

(A) ACYCLIC DIENES:

Simple alkenes such as ethylene absorbs at 175 nm (εmax 15,000). But in 1, 3-
butadiene due to the presence of two double bonds in conjugation the *
absorption band shifts to 217 nm with a simultaneous increase in the εmax to
21,000.

Explanation: A double bond consists of two -MOs-one bonding and the other
antibonding. But when two double bonds are brought into conjugation, four
new MOs are formed-two of these (1, and 2) are bonding and are occupied
by a pair of electrons each while the other two (3 and 4) are antibonding.
It is clear that, in 1, 3-butadiene the energy of lowest unoccupied molecular
orbital (LUMO), i.e.,3 decreases while that of the highest occupied molecular
orbital (HOMO), i.e., 4 increases. Due to this, the energy levels involved in
* transition now come closer and hence lesser amount of energy is
required. Further, since the energy levels come closer, their interaction in the
excited state increase and hence εmax also goes up.
Similarly, when three double bonds are brought into conjugation, the energy
gap between the HOMO and LUMO becomes still smaller and the *
absorption band shows a further bathochromic shift with a further increase in
εmax of the absorption band
(B) CYCLIC DIENES: These are of two types:

(i) Homoannular dienes:

 These are conjugated cyclic dienes having two double bonds present in the
same ring
 Due to rigidity of the ring system, such dienes exist in the s-cis (cisoid form)

(ii) Heteroannular dienes:

 These Conjugated cyclic dienes having two double bonds present in
different rings.
 Due to rigidity of the ring system, these dienes necessarily exist in the s-
trans (transoid) form:.

NOTE: Similar to acyclic dienes, homoannular dienes absorb at longer

wavelength but with lesser intensity as compared to heteroannular dienes
which absorb at shorter wavelengths but with higher intensity.
Effect af position of double bonds on λmax of cyclic dienes :

A double bond is said to be endocyclic if it lies within a particular ring and

exocyclic, if it lies outside a particular ring.

NOTE:
 It has been observed that each exocyclic double bond increases λmax of a
given cyclic conjugated diene or polyene by 5 nm.

 The position and intensity of an absorption band is influenced by the polarity

of the solvent used for running the spectrum.